Classifications

• • A—HUMAN NECESSITIES
  • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
  • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
  • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
  • A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
  • A01N43/24—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with two or more hetero atoms
  • A01N43/26—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with two or more hetero atoms five-membered rings
• • A—HUMAN NECESSITIES
  • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
  • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
  • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
  • A01N43/713—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with four or more nitrogen atoms as the only ring hetero atoms
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C317/00—Sulfones; Sulfoxides
  • C07C317/44—Sulfones; Sulfoxides having sulfone or sulfoxide groups and carboxyl groups bound to the same carbon skeleton
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C317/00—Sulfones; Sulfoxides
  • C07C317/44—Sulfones; Sulfoxides having sulfone or sulfoxide groups and carboxyl groups bound to the same carbon skeleton
  • C07C317/46—Sulfones; Sulfoxides having sulfone or sulfoxide groups and carboxyl groups bound to the same carbon skeleton the carbon skeleton being further substituted by singly-bound oxygen atoms
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D257/00—Heterocyclic compounds containing rings having four nitrogen atoms as the only ring hetero atoms
  • C07D257/02—Heterocyclic compounds containing rings having four nitrogen atoms as the only ring hetero atoms not condensed with other rings
  • C07D257/04—Five-membered rings
  • C07D257/06—Five-membered rings with nitrogen atoms directly attached to the ring carbon atom
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2601/00—Systems containing only non-condensed rings
  • C07C2601/02—Systems containing only non-condensed rings with a three-membered ring

Definitions

• the invention relates to the technical field of herbicides, in particular that of herbicides for the selective control of weeds and weeds in
• WO 2012/028579 A1 describes N- (tetrazol-5-yl) - and N- (triazol-5-yl) arylcarboxylic acid amides and their use as herbicides.
• the active ingredients described there do not always have a sufficient effect against harmful plants and / or they are sometimes not sufficiently compatible with some important
• Crops such as cereals, corn and rice.
• Object of the present invention is to provide alternative herbicidal active ingredients. This task is described by the following
• N- (1-methyltetrazol-5-yl) benzoic acid amides according to the invention which carry an alkyl or cycloalkyl radical in the 2-position of the phenyl ring, an alkyl radical in the 4-position and a sulfur radical in the 3-position.
• An object of the present invention are thus N- (1-methyltetrazol-5-yl) benzoic acid amides of the formula (I) or salts thereof
• X is (C 1 -C 6 ) -alkyl or (C 3 -C 6 ) -cycloalkyl
• Z is (C 1 -C 6 ) -alkyl
• R represents (Ci-C 6) -alkyl, (C3-C6) -cycloalkyl, (C3-C6) cycloalkyl (Ci-C 6) alkyl, (Ci- C6) alkyl-O- (C -C 6 ) alkyl, n is 1 or 2.
• alkyl radicals having more than two carbon atoms may be straight-chain or branched.
• Alkyl radicals mean e.g. Methyl, ethyl, n- or i-propyl, n-, i-, t- or 2-butyl, pentyls, hexyls, such as n-hexyl, i-hexyl and 1, 3-dimethylbutyl.
• Cycloalkyl means a carbocyclic saturated ring system having three to six C atoms, e.g. Cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl.
• the compounds of the general formula (I) can exist as stereoisomers. For example, if one or more asymmetrically substituted carbon atoms are present, enantiomers and diastereomers may occur. Likewise, stereoisomers occur when n is 1
• stereoisomers can be prepared by using stereoselective reactions using optically active starting materials and / or
• the invention also relates to all stereoisomers and mixtures thereof which are of the general formula (I), but not specifically defined.
• the compounds of formula (I) can form salts. Salt formation can through
• Suitable bases are organic amines, such as trialkylamines, morpholine, piperidine and pyridine, and ammonium, alkali metal or alkaline earth metal hydroxides, carbonates
• alkylsulfonium and alkylsulfoxonium salts such as (C 1 -C 4 ) -trialkylsulfonium and (C 1 -C 4 ) -trialkylsulfoxonium salts.
• R is methyl, ethyl, cyclopropyl, cyclopropylmethyl or methoxyethyl, n is 1 or 2.
• 1-bromo-3-fluorobenzene is subjected to lithiation, which is directed to the 2-position.
• the carbanion is then converted to the thioether.
• the benzoic acid is converted via an ortho-directing lithiation mediated by the fluorine atom with subsequent carboxylation
• the fluorine atom can be exchanged nucleophilicly for alkyl or cycloalkyl radicals (AI Meyers et al., Tetrahedron Letters, 1978, 3, 223-226; Al Meyers et al., Tetrahedron, 1994, 50 (8), 2297-2360; TW Greene, PGM Wuts, Protective Groups in Organic Synthesis, 2nd Edition, John Wiley & Sons, Inc. 1991, p. 265 et seq .; Z. Hell et al., Tetrahedron Letters, 2002, 43, 3985-3987.).
• the subsequent oxazoline cleavage provides the substituted 4-bromo-3-methylthiobenzoic acid, which is subjected to cross-coupling as the methyl ester.
• the thioether can be further oxidized to the corresponding sulfoxide or sulfone (Scheme 2).
• Oxidation methods which lead selectively to the sulfoxide or sulfone are known in the literature.
• n 1 or 2
• benzoic acids of the formula (II) and benzoic acid chlorides of the formula (III) used as intermediates in the preparation of the compounds of the formula (I) according to the invention are novel and likewise an object of the present invention.
• the listed equipment leads to a modular procedure, in which the individual work steps are automated, but between the work steps, manual operations must be performed.
• This can be circumvented by the use of partially or fully integrated automation systems in which the respective automation modules are operated, for example, by robots.
• Such automation systems can be obtained, for example, from Caliper, Hopkinton, MA 01748, USA.
• Synthesis methods allow a number of protocols known from the literature, which in turn can be carried out manually or automatically.
• the reactions can be carried out, for example, by means of IRORI technology in microreactors (microreactors) from Nexus Biosystems, 12140 Community Road, Poway, CA92064, USA.
• the preparation according to the methods described herein provides compounds of formula (I) and their salts in the form of substance collections called libraries.
• the present invention also provides libraries containing at least two compounds of formula (I) and their salts.
• the compounds of the invention have an excellent herbicidal
• Harmful plants that drive off rhizomes, rhizomes or other permanent organs are well detected by the active ingredients.
• the present invention therefore also provides a method for controlling unwanted plants or for regulating the growth of plants, preferably in plant crops, wherein one or more of the present invention
• Compound (s) on the plants e.g., weeds such as mono- or dicotyledons
• the compounds of the invention may be e.g. in pre-sowing (possibly also by incorporation into the soil), pre-emergence or Nachauflaufmaschine be applied.
• some representatives of the monocotyledonous and dicotyledonous weed flora can be named, which can be controlled by the compounds according to the invention, without the intention of limiting them to certain species.
• the compounds according to the invention are applied to the surface of the earth prior to germination, either the emergence of the weed seedlings is completely prevented or the weeds grow up to the cotyledon stage, but then stop their growth and finally die after three to four weeks
• the compounds of the invention have excellent herbicidal activity against mono- and dicotyledonous weeds, crops of economically important crops, e.g. dicotyledonous cultures of the genera Arachis, Beta, Brassica, Cucumis, Cucurbita, Helianthus, Daucus, Glycine, Gossypium, Ipomoea, Lactuca, Linum, Lycopersicon, Miscanthus, Nicotiana, Phaseolus, Pisum, Solanum, Vicia, or monocotyledonous genera Allium, pineapple , Asparagus, Avena, Hordeum, Oryza, Panicum, Saccharum, Seeale, Sorghum, Triticale, Triticum, Zea, especially Zea and Triticum, depending on the structure of the respective compound of the invention and their application rate only insignificantly or not at all damaged. For these reasons, the present compounds are very well suited for the selective control of undesired plant growth in
• Crops such as agricultural crops or ornamental plantings.
• the compounds of the invention depending on their respective chemical structure and the applied application rate, excellent growth regulative properties in crop plants. They regulate the plant's metabolism and can thus be used to specifically influence plant ingredients and facilitate harvesting, eg by triggering desiccation and stunted growth.
• the active compounds can also be used for controlling harmful plants in crops of known or yet to be developed genetically modified plants.
• the transgenic plants are usually characterized by particular advantageous properties, for example by resistance to certain pesticides, especially certain herbicides, resistance to plant diseases or pathogens of plant diseases such as certain insects or microorganisms such as fungi, bacteria or viruses.
• Other special special traits for example by resistance to certain pesticides, especially certain herbicides, resistance to plant diseases or pathogens of plant diseases such as certain insects or microorganisms such as fungi, bacteria or viruses.
• Properties relate to e.g. the crop in terms of quantity, quality, shelf life, composition and special ingredients.
• transgenic plants with increased starch content or altered quality of the starch or those with other fatty acid composition of the crop are known. More special
• Properties may be in tolerance or resistance to abiotic stressors, e.g. Heat, cold, drought, salt and ultraviolet radiation are present.
• abiotic stressors e.g. Heat, cold, drought, salt and ultraviolet radiation are present.
• Crop crops are used, which compared to the phytotoxic Effects of the herbicides are resistant or have been made genetically resistant.
• Glufosinate cf., for example, EP 0242236 A, EP 0242246 A
• glyphosate WO 92/000377 A
• sulfonylureas EP 0257993 A, US 5,013,659
• Transgenic crops for example cotton, with the ability to produce Bacillus thuringiensis toxins (Bt toxins), which make the plants resistant to certain pests (EP 0142924 A, EP 0193259 A).
• Bacillus thuringiensis toxins Bacillus thuringiensis toxins
• transgenic crops which are characterized by a combination of eg the above new Characterize properties ("gene stacking")
• nucleic acid molecules can be used in any genetic manipulations.
• nucleic acid molecules can be used in any genetic manipulations.
• Plasmids are introduced which allow mutagenesis or a sequence change by recombination of DNA sequences.
• Base exchanges are made, partial sequences removed or natural or synthetic sequences added.
• For the connection of the DNA fragments with one another adapters or linkers can be attached to the fragments, see e.g. Sambrook et al., 1989, Molecular Cloning, A Laboratory Manual, 2nd Ed. Cold Spring Harbor Laboratory Press, Cold Spring Harbor, NY; or Winnacker "Genes and Clones", VCH Weinheim 2nd edition 1996
• the production of plant cells having a reduced activity of a gene product can be achieved, for example, by the expression of at least one
• Cosuppressions need.es or the expression of at least one appropriately engineered ribozyme that specifically cleaves transcripts of the above gene product.
• DNA molecules may be used which comprise the entire coding sequence of a gene product, including any flanking sequences that may be present, as well as DNA molecules which comprise only parts of the coding sequence, which parts must be long enough to be present in the cells to cause an antisense effect. It is also possible to use DNA sequences which have a high degree of homology to the coding sequences of a gene product, but are not completely identical.
• the synthesized protein may be located in any compartment of the plant cell.
• the coding region can be linked to DNA sequences that ensure localization in a particular compartment.
• sequences are known to those skilled in the art (see, for example, Braun et al., EMBO J. 11 (1992), 3219-3227; Wolter et al., Proc. Natl. Acad., U.S.A. 85 (1988), 846-850; Sonnewald et al., Plant J. 1 (1991), 95-106).
• Expression of the nucleic acid molecules can also be found in the
• Organelles of the plant cells take place.
• the transgenic plant cells can be regenerated to whole plants by known techniques.
• the transgenic plants may, in principle, be plants of any plant species, that is, both monocotyledonous and dicotyledonous plants.
• transgenic plants are available, the altered properties by
• Cultures are used, which against growths, such. 2,4 D, dicamba or against herbicides containing essential plant enzymes, e.g. Acetolactate synthases (ALS), EPSP synthases, glutamine synthases (GS) or Hydoxyphenylpyruvat Dioxygenases (HPPD) inhibit or resistant to herbicides from the group of sulfonylureas, the glyphosate, glufosinate or Benzoylisoxazole and analogues, or against any combination of these agents resistant.
• ALS Acetolactate synthases
• EPSP synthases e.g., EPSP synthases
• G glutamine synthases
• HPPD Hydoxyphenylpyruvat Dioxygenases
• the compounds according to the invention can particularly preferably be employed in transgenic crop plants which are resistant to a combination of glyphosates and glufosinates, glyphosates and sulfonylureas or imidazolinones. Very particular preference may be given to the compounds according to the invention in
• transgenic crops such as corn or soybean with the trade name or the name Optimum TM GAT TM (Glyphosate ALS Tolerant) are used.
• Optimum TM GAT TM Glyphosate ALS Tolerant
• Harmful plants often have effects that are specific for application in the particular transgenic culture, such as altered or specially extended weed spectrum that can be controlled
• the invention therefore also relates to the use of the compounds of the formula (I) according to the invention as herbicides for controlling harmful plants in transgenic crop plants.
• the compounds of the invention may be in the form of wettable powders
• the invention therefore also relates to herbicidal and plant growth-regulating agents which contain the compounds according to the invention.
• the compounds according to the invention can be formulated in various ways, depending on which biological and / or chemical-physical parameters are predetermined. Possible formulation options are, for example: wettable powder (WP), water-soluble powders (SP), water-soluble concentrates,
• EC emulsifiable concentrates
• EW emulsions
• Water-in-oil emulsions sprayable solutions, suspension concentrates (SC), oil- or water-based dispersions, oil-miscible solutions, capsule suspensions (CS), dusts (DP), mordants, granules for spreading and soil application, granules (GR) in the form of micro, spray, elevator and adsorption granules, water-dispersible granules (WG), water-soluble granules (SG),
• Injectable powders are preparations which are uniformly dispersible in water and contain surfactants of the ionic and / or nonionic type (wetting agents, dispersants) in addition to the active ingredient except a diluent or inert substance.
• surfactants of the ionic and / or nonionic type (wetting agents, dispersants) in addition to the active ingredient except a diluent or inert substance.
• the herbicidal active compounds are finely ground, for example, in customary apparatus such as hammer mills, blower mills and air-jet mills and mixed simultaneously or subsequently with the formulation auxiliaries.
• Emulsifiable concentrates are made by dissolving the active ingredient in one
• organic solvents e.g. Butanol, cyclohexanone, dimethylformamide, xylene or higher-boiling aromatics or hydrocarbons or mixtures of organic solvents with the addition of one or more surfactants of ionic and / or nonionic type (emulsifiers).
• emulsifiers which may be used are: alkylarylsulfonic acid calcium salts, such as
• Ca-dodecylbenzenesulfonate or nonionic emulsifiers such as
• Fatty acid polyglycol esters alkylaryl polyglycol ethers, fatty alcohol polyglycol ethers, Propylene oxide-ethylene oxide condensation products, alkyl polyethers, sorbitan esters such as sorbitan fatty acid esters or Polyoxethylensorbitanester such as
• Dusts are obtained by milling the active ingredient with finely divided solids, e.g. Talc, natural clays such as kaolin, bentonite and pyrophyllite, or diatomaceous earth.
• finely divided solids e.g. Talc, natural clays such as kaolin, bentonite and pyrophyllite, or diatomaceous earth.
• Suspension concentrates may be water or oil based. They can be prepared, for example, by wet grinding using commercially available bead mills and, if appropriate, addition of surfactants, as described, for example, in US Pat. upstairs with the others
• Emulsions e.g. Oil-in-water emulsions (EW) can be prepared, for example, by means of stirrers, colloid mills and / or static mixers using aqueous organic solvents and optionally surfactants, as described e.g. listed above for the other formulation types.
• EW Oil-in-water emulsions
• Granules can be prepared either by spraying the active ingredient on adsorptive, granulated inert material or by applying
• Active substance concentrates by means of adhesives, e.g. Polyvinyl alcohol, polyacrylic acid sodium or mineral oils, on the surface of carriers such as sand, kaolinites or granulated inert material. It is also possible to granulate suitable active ingredients in the manner customary for the production of fertilizer granules, if desired in admixture with fertilizers.
• adhesives e.g. Polyvinyl alcohol, polyacrylic acid sodium or mineral oils
• carriers such as sand, kaolinites or granulated inert material. It is also possible to granulate suitable active ingredients in the manner customary for the production of fertilizer granules, if desired in admixture with fertilizers.
• Water-dispersible granules are generally prepared by the usual methods such as spray drying, fluidized bed granulation, plate granulation, mixing with high-speed mixers and extrusion without solid inert material.
• spray drying fluidized bed granulation
• plate granulation mixing with high-speed mixers and extrusion without solid inert material.
• the agrochemical preparations generally contain from 0.1 to 99% by weight, in particular from 0.1 to 95% by weight, of compounds according to the invention.
• the drug concentration is e.g. about 10 to 90 wt .-%, the balance to 100 wt .-% consists of conventional formulation ingredients.
• the active ingredient concentration may be about 1 to 90, preferably 5 to 80 wt .-%.
• Dust-like formulations contain 1 to 30 wt .-% of active ingredient, preferably usually 5 to 20 wt .-% of active ingredient, sprayable solutions contain about 0.05 to 80, preferably 2 to 50 wt .-% of active ingredient.
• the active ingredient content depends, in part, on whether the active compound is liquid or solid and which
• Granulation aids, fillers, etc. are used. In the water
• the content of active ingredient is for example between 1 and 95 wt .-%, preferably between 10 and 80 wt .-%.
• the active substance formulations mentioned optionally contain the customary adhesive, wetting, dispersing, emulsifying, penetrating, preserving,
• Evaporation inhibitors and pH and viscosity affecting agents are optionally diluted in a customary manner, e.g. for wettable powders, emulsifiable concentrates, dispersions and water-dispersible granules by means of water. Dust-like preparations, ground or scattered granules and sprayable solutions are usually no longer diluted with other inert substances before use.
• the required application rate of the compounds of the formula varies (I). It can vary within wide limits, eg between 0.001 and 1.0 kg / ha or more of active substance, but is preferably between 0.005 and 750 g / ha.
• Tetrahydrofuran added dropwise.
• the solution was stirred at -78 ° C for 1.5 h. Thereafter, 298 g (6.78 mol) of carbon dioxide was added as dry ice.
• Step 3 Synthesis of 4-bromo-2-fluoro-N- (1-hydroxy-2-methylpropan-2-yl) -3-
• Step 4 Synthesis of 2- [4-Bromo-2-fluoro-3- (methylsulfanyl) phenyl] -4,4-dimethyl-4,5-dihydro-1,3-oxazole
• Crude product was recrystallized from diisopropyl ether to isolate 165 g of the desired product.
• Step 5 Synthesis of 2- [4-bromo-2-methyl-3- (methylsulfanyl) phenyl] -4,4-dimethyl-4,5-dihydro-1,3-oxazole
• Tetrahydrofuran added. The mixture was stirred at room temperature until the lithium chloride was dissolved. Subsequently, 200 ml (1 M, 200 mmol) of a solution of methylmagnesium bromide in tetrahydrofuran were added. The mixture was then cooled to -20 ° C. At this temperature, 228 ml (0.7M, 160 mmol) of a solution of zinc chloride in dry tetrahydrofuran were slowly added dropwise. The mixture was stirred for a further 10 minutes at this temperature. The contents were then thawed to room temperature and stirred for a further 1 h. Thereafter, vacuum was repeatedly applied to the reaction flask to remove oxygen and vented with argon.
• Step 9 Synthesis of 2,4-dimethyl-3- (methylsulfanyl) -N- (1-methyl-1H-tetrazol-5-yl) -benzamide
• Step 10 Synthesis of 2,4-dimethyl-3- (methylsulfinyl) -N- (1-methyl-1H-tetrazol-5-yl) -benzamide
• NMR data in the so-called NMR peak list method.
• the 1 H NMR data of selected examples are recorded in the form of 1 H NMR peaks. For each signal peak, first the ⁇ value in ppm and then the signal intensity in parentheses are listed. The ⁇ -value signal intensity number pairs of different signal peaks are listed separated by semicolons.
• the peak list of an example therefore has the form:
• the intensity of sharp signals correlates with the height of the signals in a printed example of an NMR spectrum in cm and shows the true ratios of the signal intensities. For broad signals, multiple peaks or the center of the signal and their relative intensity can be shown compared to the most intense signal in the spectrum.
• the lists of the 1 H NMR peaks are similar to the classical 1 H NMR prints and thus usually contain all the peaks listed in a classical NMR interpretation. In addition, they can, like classical 1 H NMR prints solvent signals, signals from stereoisomers of the
• Target compounds which are also the subject of the invention, and / or show peaks of impurities.
• Such stereoisomers and / or impurities may be typical of the particular preparation process. Their peaks can thus help to detect the reproduction of our manufacturing process by "by-product fingerprints.”
• a dust is obtained by mixing 10 parts by weight of a compound of formula (I) and / or salts thereof and 90 parts by weight of talc as an inert material and comminuting in a hammer mill.
• a wettable powder readily dispersible in water is obtained by reacting 25 parts by weight of a compound of the formula (I) and / or its salts, 64 parts by weight of kaolin-containing quartz as inert material, 10 parts by weight
• a dispersion concentrate readily dispersible in water is obtained by reacting 20 parts by weight of a compound of the formula (I) and / or salts thereof with 6 parts by weight of alkylphenol polyglycol ether ( ⁇ Triton X 207), 3 parts by weight
• Mineral oil (boiling range, for example, about 255 to about 277 C) mixed and ground in a ball mill to a fineness of less than 5 microns,
• a water-dispersible granule is also obtained by
• the compounds according to the invention formulated in the form of wettable powders (WP) or as emulsion concentrates (EC) are then used as aqueous suspension or
• the compounds according to the invention formulated in the form of wettable powders (WP) or as emulsion concentrates (EC) are then used as aqueous suspension or

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Life Sciences & Earth Sciences (AREA)
• Agronomy & Crop Science (AREA)
• Pest Control & Pesticides (AREA)
• Plant Pathology (AREA)
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• Engineering & Computer Science (AREA)
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• General Health & Medical Sciences (AREA)
• Wood Science & Technology (AREA)
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• Agricultural Chemicals And Associated Chemicals (AREA)

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